US4472261A - Dissolved oxygen gas measuring electrode system - Google Patents

Dissolved oxygen gas measuring electrode system Download PDF

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Publication number
US4472261A
US4472261A US06/482,556 US48255683A US4472261A US 4472261 A US4472261 A US 4472261A US 48255683 A US48255683 A US 48255683A US 4472261 A US4472261 A US 4472261A
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United States
Prior art keywords
electrode
membrane
indicator
shaft
electrode system
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Expired - Fee Related
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US06/482,556
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English (en)
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Masahiro Oita
Naohumi Tonoka
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Assigned to MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD. reassignment MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OITA, MASAHIRO, TONOKA, NAOHUMI
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/38—Cleaning of electrodes

Definitions

  • This invention relates to an electrode system for measuring oxygen gas concentration in a solution, especially in blood.
  • Determination of oxygen gas in blood has been conducted in clinical fields including diagnosis of various diseases of circulatory and respiratory organs, the examination of endocrine, metabolic, and digestive organ diseases, nacotism, and the control of respiratory function after operations.
  • Much attention has been paid to oxygen concentration in blood of babies born immature and infants in a syncopic state. When oxygen is lacking in the blood it does not reach all parts of the body resulting in death or suffering from cerebral palsy. Conversely, if oxygen in the blood is in great excess it is responsible for diseases like retinitis (in immature babies).
  • U.S. Pat. No. 2,913,386 discloses an electrolytic device called a "CLARK ELECTRODE" for use in chemical analysis, and particularly a polarographic cell adaptable for use in making quantitative analysis, especially continuous analysis. It comprises an electrode pair supported in a predetermined spaced relationship and electrically connected by an electrolyte or a substance reactable to form an electrolyte, and a selectively permeable barrier for separating the electrode pair and the electrolyte or other substance from the composition to be analyzed.
  • U.S. Pat. No. 3,372,103 discloses an improved dissolved oxygen probe in order to obtain a fast response, a stable reading and a long performance life.
  • the surface of a lead anode is large relative to that of a platinum cathode, at least 30 to 1.
  • the surface area of the lead rod in square inches relative to the volume of electrolyte in milliliters is greater than one.
  • U.S. Pat. No. 3,088,905 discloses an electrode system which is not affected by solution movement and other constituents in the test solution, for example proteins in blood or metal ions in industrial solutions.
  • the negative electrode consisting of a platinum or gold wire is fixed co-axially within a silver tube acting as the positive electrode by means of an electrically insulating material such as glass, filling the space between the wire and tube. The whole thus forms a solid rod, one end of which is ground flat.
  • a sample solution to be analyzed is located on the other side of the membrane. Since a voltage of 0.4 volt to 0.8 volt is applied between the two electrodes, oxygen penetrating through the membrane is electrolized, resulting in a flowing polarographic current proportional to the concentration of oxygen in the sample solution.
  • Ag/AgCl or Ag is used as a reference electrode.
  • Concerning the Ag/AgCl electrode its surface turns into an silver chloride rich electrode through electrolysis because of the dissolving of silver.
  • silver deposits on the surface of the indicator electrode.
  • FIG. 1 is a cross-sectional view of an embodiment of an oxygen gas electrode system having a rotating membrane according to the present invention.
  • FIG. 2 is a cross-sectional view of an embodiment of a membrane-rotating electrode system for a flow-through analysis according to the present invention.
  • FIG. 3 is an enlarged fragmentary detail cross-sectional view of an embodiment of an electrode system according to the present invention.
  • FIG. 4 is a cross-sectional view of an embodiment of an electrode shaft-rotating electrode system according to the present invention.
  • FIG. 5 is a cross-sectional view of an embodiment of an electrode shaft-rotating electrode system for continuous measurement according to the present invention.
  • FIG. 1 A cross-sectional view of an oxygen gas measuring electrode system according to the present invention is shown in FIG. 1.
  • An electrode shaft 4 is prepared in such a manner that an indicator electrode 1 of a precious metal such as gold and platinum is mounted on an end surface of shaft 4 covered by an insulating material 2 (made of such a material as plastic).
  • An annular reference electrode 3 such as silver-silver chloride is mounted on the side surface of shaft 4 so as to surround shaft 4.
  • Lead wires 1' and 3' running inside shaft 4 are connected with indicator electrode 1 and reference electrode 3, respectively so as to obtain electric signals from the electrodes.
  • Electrode shaft 4 is attached to a bottom opening of an electrolytic cell 5 having an inlet 7 and an outlet 8 for an electrolyte solution 6 such as phosphite buffer solution. Accordingly, shaft 4 is immersed in solution 6.
  • Electrolysis of oxygen takes place between electrodes 1 and 3.
  • the measurement of oxygen in a solution requires an oxygen permeable membrane 11, such as fluoride resin (i.e. Teflon), polycarbonate, polyethylene or polypropylene, which allows oxygen gas to pass through independently of the perviousness of any solution.
  • an oxygen permeable membrane 11 such as fluoride resin (i.e. Teflon), polycarbonate, polyethylene or polypropylene, which allows oxygen gas to pass through independently of the perviousness of any solution.
  • a membrane conventionally used, is so thin and easily damaged that reinforcement is necessary to make it easy to handle.
  • the periphery of membrane 11 is sandwiched between supporting materials consisting of two gear wheels 16 and 17, which are bound with screws 14 and 15. Otherwise, an adhesive may be applied between membrane 11 and gear wheels 16 and 17.
  • Membrane 11, having the above mentioned reinforced periphery is mounted on the top opening of the electrolytic cell 5 to cover indicator electrode 1, so that indicator electrode 1 is pressed lightly against membrane 11.
  • a circular projection 21 is formed on the top surface of electrolytic cell 5 so as to serve as a guide for rotation of gear wheels 16 and 17.
  • Projection 21 is fitted to a circular groove 18 of gear wheel 16.
  • gear wheel 17 also has a groove 19 in which is inlaid a projection 22 of a ring 23 which constitutes a test chamber 24.
  • a gap between gear wheel 17 and ring 23 is mechanically sealed so as to prevent sample solution from leaking.
  • the same is the case for a gap between gear wheel 16 and cell 5 so as to prevent the leaking of electrolytic solution 6.
  • the polarographic current is proportional to the oxygen content in the sample solution.
  • silvering takes place on the surface of indicator electrode 1.
  • a contrivance to eliminate the silver from the surface of the indicator electrode is an important point of the present invention.
  • the surface of the indicator electrode 1 is kept constantly clean by being rubbed with the membrane.
  • the electrode system of the present invention gives a stable reading, has a long performance life, and shows good reproducibility of measurement values.
  • FIG. 2 Another embodiment of the electrode system for flow-through measurement according to the present invention is shown in FIG. 2 as a modification of the electrode system illustrated in FIG. 1.
  • a cap 40 having a channel 41 is mounted on gear wheel 17.
  • a sample solution flows from an inlet 43 to an exit 44.
  • a space defined by cap 40 and membrane 11 constitutes a sample chamber 42 for the flow-through measurement.
  • Membrane 11 having thereunder a mesh 45, made of a material such as nylon or cotton, which directly contacts the surface of indicator electrode 1 is sandwiched between two gear wheels 16 and 17. This arrangement prevents the membrane 11 from wearing since the membrane 11 does; not directly contact the electrode 1. This allows carrying out continuous analysis of dissolved oxygen for a long period of time without exchanging membrane 11.
  • An aperture 46 running through the inside of electrode shaft 4 serves as an inlet for electrolyte solution 6. Injecting electrolyte 6 from the aperture 46 can avoid the occurrence of air bubbles remaining on the surface of indicator electrode 1. During the analysis of oxygen such air bubbles render measurement values inaccurate and unstable. A main disadvantage of the deposition of silver on indicator electrode 1 has already been described.
  • FIG. 3 A fragmentary view of a modified embodiment of the electrode system considering the above measures is shown in FIG. 3.
  • a magnetic stirrer 55 is placed in a test chamber 42 and rotated on membrane 11 by means of a magnet 50 attached to an axle 51 of a motor (not shown).
  • a buffer consisting of a polishing rod 52 and a spring 53 for pushing rod 52 is attached to gear wheel 16.
  • reference electrode 3 tightly contacting polishing rod 52, can be constantly polished so that the surface of electrode 3 is kept clean.
  • FIG. 4 illustrates a vertical cross section of a further embodiment of an electrode system according to the present invention, in which electrode shaft 4 is rotated and membrane 11 is fixed.
  • indicator electrode 1 is mounted on the end surface of electrode shaft 4.
  • ring shaped reference electrode 3 is mounted on the side surface of shaft 4.
  • This shaft 4 is placed in electrolytic cell 5 which has top and bottom openings. A portion of shaft 4 sticks out through the bottom opening which is therein provided with a bearing 66 and an oil seal 67 for preventing electrolyte solution 6 from leaking through the opening during the rotation of shaft 4.
  • oil seal 67 a mechanical seal may be used.
  • a conventional motor (not shown) is installed to rotate shaft 4 which is clutched at a motor axle 68.
  • Lead wire 1' links indicator electrode 1 to a circular electric contact 1" mounted around the side surface of shaft 4.
  • Lead wire 3' links reference electrode 3 to another electric contact 3" mounted around the side surface of shaft 4.
  • Membrane 11 with its periphery reinforced is fixed in the upper opening of cell 5 with screws 64 and 65 so as to lightly contact the surface of indicator electrode 1.
  • a gasket or an O-ring (not shown) between the periphery thereof for holding membrane 11 and the top surface of cell 5 so as to prevent electrolyte solution 6 from oozing out.
  • the surface of indicator electrode 1 is constantly rubbed by membrane 11 while shaft 4 rotates. The instant silver is deposited on the surface of indicator electrode 1, it is immediately eliminated from the surface. Consequently, indicator electrode 1 is substantially maintained in its initial state without any contamination by deposited silver.
  • FIG. 5 Still another preferable embodiment of an electrode system according to the prevent invention is shown in FIG. 5.
  • this electrode system not merely indicator electrode 1, but reference electrode 3 and membrane 11 as well, are constantly kept clean.
  • reference electrode 3 its surface is polished by means of a buffer.
  • the buffer which is attached in the side wall of electrolytic cell 5 comprises rod 52 of a polishing agent made of a material such as resin, SiC and buffing cloth, spring 53 for pushing rod 52 from behind and a container 70 for accommodating them. Spring 53 constantly presses polishing rod 52 so that reference electrode 3 comes in close contact with rod 52. Even in continuous measurement, this system helps reference electrode 3 maintain the same activity as it initially has.
  • Magnetic stirrer 55 coated with resin for preventing it from rusting is placed in sample chamber 42. Stirrer 55 rotates and constantly rubs the surface of membrane 11 by means of magnet 50 attached to motor axle 68 which is linked to electrode shaft 4. Thus, even if a test solution is blood which is easily coagulates on membrane 11, its surface can be maintained as clean as it originally is.
  • the electrode system hereinbefore described is not restricted only to vertical use. But it can be used tilted, horizontally and upside down.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
US06/482,556 1982-04-09 1983-04-06 Dissolved oxygen gas measuring electrode system Expired - Fee Related US4472261A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57-59994 1982-04-09
JP57059994A JPS58176539A (ja) 1982-04-09 1982-04-09 血中酸素ガス濃度測定用電極

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701252A (en) * 1982-06-16 1987-10-20 Matsushita Electric Industrial Co., Ltd. Dissolved gas and ion measuring electrode system
AU594766B2 (en) * 1986-04-07 1990-03-15 Katalistiks International, Inc. Metal-containing spinel composition and process of using same
EP2947451A4 (en) * 2013-01-18 2016-08-17 Sony Corp DEVICE FOR MEASURING ELECTRICAL CHARACTERISTICS
EP3399308B1 (en) * 2017-05-05 2023-06-07 NeoSense Technologies AB Oxygen sensor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172725A3 (en) * 1984-08-22 1987-08-26 Noel Bibby Limited Measuring water vapour transmission through materials

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1668434A (en) * 1926-11-23 1928-05-01 Emery W Todd Liquid-testing apparatus
US3070539A (en) * 1960-01-25 1962-12-25 Beckman Instruments Inc Ionic transducer
US3073772A (en) * 1959-04-10 1963-01-15 Polymetron A G Apparatus for continuously measuring the potential in a liquid and for simultaneously cleaning the measuring electrode
US3155603A (en) * 1962-09-12 1964-11-03 Dow Chemical Co Antimony electrode assembly
US3235477A (en) * 1962-10-12 1966-02-15 Honeywell Inc Electrical apparatus
US3402116A (en) * 1963-10-12 1968-09-17 Fischer & Porter Co Apparatus for the measurement of residual chlorine or the like
US3496084A (en) * 1967-11-21 1970-02-17 Weston & Stack Inc Dissolved oxygen probe and agitator assembly
US3563875A (en) * 1968-04-02 1971-02-16 Dale M Coulson Apparatus for coulometric titration
US3574079A (en) * 1968-03-14 1971-04-06 Foerderung Forschung Gmbh Apparatus for oxygen determination
US3718567A (en) * 1970-04-07 1973-02-27 Instrumentation Labor Inc Electrode assembly
US4019966A (en) * 1974-06-04 1977-04-26 Vyzkumny Ustav Organickych Syntex Method of amperometric determination of the concentration of arendiazonium salts

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1668434A (en) * 1926-11-23 1928-05-01 Emery W Todd Liquid-testing apparatus
US3073772A (en) * 1959-04-10 1963-01-15 Polymetron A G Apparatus for continuously measuring the potential in a liquid and for simultaneously cleaning the measuring electrode
US3070539A (en) * 1960-01-25 1962-12-25 Beckman Instruments Inc Ionic transducer
US3155603A (en) * 1962-09-12 1964-11-03 Dow Chemical Co Antimony electrode assembly
US3235477A (en) * 1962-10-12 1966-02-15 Honeywell Inc Electrical apparatus
US3402116A (en) * 1963-10-12 1968-09-17 Fischer & Porter Co Apparatus for the measurement of residual chlorine or the like
US3496084A (en) * 1967-11-21 1970-02-17 Weston & Stack Inc Dissolved oxygen probe and agitator assembly
US3574079A (en) * 1968-03-14 1971-04-06 Foerderung Forschung Gmbh Apparatus for oxygen determination
US3563875A (en) * 1968-04-02 1971-02-16 Dale M Coulson Apparatus for coulometric titration
US3718567A (en) * 1970-04-07 1973-02-27 Instrumentation Labor Inc Electrode assembly
US4019966A (en) * 1974-06-04 1977-04-26 Vyzkumny Ustav Organickych Syntex Method of amperometric determination of the concentration of arendiazonium salts

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701252A (en) * 1982-06-16 1987-10-20 Matsushita Electric Industrial Co., Ltd. Dissolved gas and ion measuring electrode system
AU594766B2 (en) * 1986-04-07 1990-03-15 Katalistiks International, Inc. Metal-containing spinel composition and process of using same
EP2947451A4 (en) * 2013-01-18 2016-08-17 Sony Corp DEVICE FOR MEASURING ELECTRICAL CHARACTERISTICS
EP3399308B1 (en) * 2017-05-05 2023-06-07 NeoSense Technologies AB Oxygen sensor

Also Published As

Publication number Publication date
JPH0153418B2 (en]) 1989-11-14
DK156883D0 (da) 1983-04-08
JPS58176539A (ja) 1983-10-17
DK156883A (da) 1983-10-10

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